ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSKBAHRIS..MTNORSMESMMAKHTNMD..........
J
2.0.21 - 1100000/0
4203038
EUROPEAN PATENT APPLICATION
A1
20230628
EP
21216277.0
20211221
en
en
en
20230628
202326
20230628
202326
H01L 27/11507 20170101AFI20220513BHEP
H01L 49/02 20060101ALI20220513BHEP
H01L 27/1159 20170101ALI20220513BHEP
H01L 28/40 20130101 FI20220506BHEP
H10B 53/30 20230201 LA20230201BHEP
H10B 51/30 20230201 LA20230201BHEP
H01L 28/56 20130101 LA20230201BHEP
de
FERROELEKTRISCHE VORRICHTUNG
en
FERROELECTRIC DEVICE
fr
DISPOSITIF FERROÉLECTRIQUE
1a
IMEC VZW
101121283
EP-21131572
Kapeldreef 75
3001 Leuven
BE
POPOVICI, Mihaela Ioana
3053 Haasrode
BE
VAN HOUDT, Jan
3460 Bekkevoort
BE
WALKE, Amey Mahadev
3001 Heverlee
BE
KAR, Gouri Sankar
3001 Leuven
BE
BIZINDAVYI, Jasper
3000 Leuven
BE
AWA Sweden AB
101871851
Box 5117
200 71 Malmö
SE
AL
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TN
According to an aspect of the present inventive concept there is provided a ferroelectric device layer structure (10) comprising: a first electrode (12) and a second electrode (13); a ferroelectric layer (11) of hafnium zirconate, HZO; and an oxide layer (21) of Nb_2O_5 or Ta_2O_5 arranged on the ferroelectric layer (11); wherein the ferroelectric layer (11) and the oxide layer (21) are arranged between the first electrode (12) and the second electrode (13).
A ferroelectric device (20) comprising the layer structure (10) and a method (100) for fabricating a ferroelectric device are also provided.

Technical field
The present inventive concept relates to a ferroelectric device layer structure that may be comprised in a ferroelectric device, for instance, a metal-ferroelectric-metal (MFM) capacitor, a ferroelectric random access memory (Fe-RAM), or a ferroelectric field effect transistor (FeFET). The ferroelectric device is based on hafnium zirconate (HZO) and either Nb_2O_5 or Ta_2O_5, i.e., it comprises a HZO layer and a layer of Nb_2O_5 or Ta_2O_5. The present disclosure also relates to a method of manufacturing such a ferroelectric device.

Background
A non-volatile data storage (generally, a memory device) can be obtained using ferroelectric oxides, due to their capacity to store binary information in two distinct polarization states. These polarization states arise, for example,
in hafnium oxide (HfO_2) and in HZO. The cause of these polarization states is the formation of a non-centrosymmetric polar orthorhombic Pca21 phase (short "orthorhombic crystal structure"), with four oxygen atoms in a unit cell that have two stable positions.
A large memory window requires a high remnant polarization (2P_R) of the ferroelectric oxide, which should be at least 10 µC/cm^2, and also requires a high endurance in order to maintain such a high 2P_R for at least 1E+9 cycles (for around 10 years lifetime) of the memory device. The fatigue is a degradation phenomenon in the ferroelectric oxide, which causes the remnant polarization of the ferroelectric oxide to decrease. The endurance is a measure of how many times the ferroelectric oxide can be cycled (i.e., switched between the two distinct polarization states), until significant fatigue sets in (which may make the two polarization states less distinct), i.e. it suffers a permanent breakdown.
It would be desirable to stabilize the orthorhombic crystal structure for a fatigue-free high endurance and a high remnant polarization.

Summary
An objective of the present inventive concept is to provide an improved ferroelectric device layer structure.
According to an aspect of the present inventive concept there is provided a ferroelectric device layer structure comprising: a first electrode and a second electrode; a ferroelectric layer of hafnium zirconate, HZO; and an oxide layer of Nb_2O_5 or Ta_2O_5 arranged on the ferroelectric layer; wherein the ferroelectric layer and the oxide layer are arranged between the first electrode and the second electrode.
By the oxide layer being arranged on the ferroelectric layer, the oxide layer may be above, below, or both above and below the ferroelectric layer compared to a stacking direction of the layer structure, e.g. in relation to a substrate.
The oxide layer(s) are arranged in direct contact with the ferroelectric layer, i.e. without any interfacial layer(s) in between.
The oxide layer being Nb_2O_5 or Ta_2O_5 enables an oxygen-rich interfacial layer between the ferroelectric layer and an electrode, which prevents oxygen scavenging by the electrode. Accordingly, endurance is improved.
The oxide layer being Nb_2O_5 or Ta_2O_5 further enables an enhanced in-plane tensile strain in the ferroelectric layer based on a lattice mismatch between the oxide layer and the ferroelectric layer. Accordingly, remnant polarization is increased.
The oxide layer being Nb_2O_5 or Ta_2O_5 further enables having fewer pinned domains in the ferroelectric layer, which improves wake-up characteristics from the pristine state (i.e. no cycling yet).
Typically, (doped) HZO shows pinched polarization vs electrical field (E-field) loops (PE-loop) as a result of the pinning of (some fraction of) the ferroelectric domains due to local E-field variations that arise from the presence of pinning centers (e.g. defects) inside the HZO layer. These pinched PE-loops typically result in very small values of 2P_R (remnant polarization). The Introduction of Nb_2O_5 or Ta_2O_5 as a capping layer on top of the (doped) HZO layer reduces the fraction of initially pinned ferroelectric domains, thereby allowing for a more open (i.e. less pinched) PE-loop and a higher 2P_R in the pristine state.
According to one embodiment at least 30% of the ferroelectric layer and the oxide layer has an orthorhombic crystal structure.
This enables more of the ferroelectric layer to be stabilized with an orthorhombic crystal structure, thereby further improving remnant polarization.
According to one embodiment the device layer structure further comprises an interfacial layer, which is arranged between the oxide layer and the second electrode.
The interfacial layer may play the role of a channel in high density and low power consumption non-volatile memories, such as a FeFET. The interfacial layer may further prevent oxygen scavenging by the electrode, thereby mitigating fatigue,
According to one embodiment the ferroelectric layer is a doped HZO layer.
The dopants may e.g. be La, Gd, Y, etc.
Dopants may further stabilize the orthorhombic crystal structure to minimize or prevent fatigue, reduce leakage, extend endurance and improve remnant polarization.
According to one embodiment the oxide layer is between 0.5-3 nm thick.
Such a thickness has shown to provide the least fatigue and longer endurance.
According to another aspect of the present inventive concept is provided a ferroelectric device comprising the layer structure according to the previous aspect. The ferroelectric device further comprises a doped semiconductor substrate having a front side and a back side, wherein the layer structure is arranged on the front side.
This aspect may generally present the same or corresponding advantages as the former aspect.
An aluminium layer may be arranged on the back side. The aluminium layer may reduce contact issues when performing electrical measurements.
According to another aspect of the present inventive concept is provided a method for fabricating a ferroelectric device. The method comprises: forming a ferroelectric device layer structure comprising: a first electrode and a second electrode; a ferroelectric layer of hafnium zirconate, HZO; and an oxide layer of Nb_2O_5 or Ta_2O_5 arranged on the ferroelectric layer; wherein the ferroelectric layer and the oxide layer are arranged between the first electrode and the second electrode. The method further comprises: annealing the layers of the ferroelectric device layer structure at a temperature in a range of 350°C - 750°C if the oxide layer is made of Nb_2O_5 and in a range of 350°C - 900°C if the oxide layer is made of Ta_2O_5.
This aspect may generally present the same or corresponding advantages as the former aspects.
After the annealing, the layers of the device layer structure may be completely crystallized.
By annealing both the oxide layer and the ferroelectric layer at the same time, they are simultaneously crystallized, which enables more of the ferroelectric layer to be stabilized with an orthorhombic crystal structure, thereby further improving remnant polarization.
According to one embodiment forming a ferroelectric device layer structure comprises: depositing a metal for forming the first electrode on a front side of a semiconductor substrate; depositing HZO for forming the ferroelectric layer on the first electrode; depositing Nb_2O_5 or Ta_2O_5 for forming the oxide layer on the ferroelectric layer; and then depositing a metal for forming the second electrode.
By depositing the layers of the device layer structure accordingly, a preferred ordering of the layers is enabled. This is because growing Nb_2O_5 or Ta_2O_5 on a metal forming the electrodes, the (Nb or Ta)/O atomic ratio may be different than when growing on HZO. This may affect the stoichiometry and crystal structure causing less of the oxide layer to be Nb_2O_5 or Ta_2O_5 (with pentavalent cations) or in an orthorhombic crystal structure.
According to one embodiment the method further comprises forming an aluminium layer on a back side of the semiconductor substrate
The aluminium layer may reduce contact issues when performing electrical measurements.
According to one embodiment the depositing steps use atomic layer deposition, ALD.
Any type of ALD may be used, such as plasma enhanced ALD and/or thermal ALD.
By using ALD for the depositing steps, the entire ferroelectric device may be fabricated using ALD, which simplifies manufacturing.
According to one embodiment the ALD is performed with a reactor temperature in a range of 150°C - 450°C.
The temperature used may depend on the precursors used in the depositing steps. Notably, each of the above layers may be deposited at a different temperature, as long as all the layers are deposited within the specified temperature range.
According to one embodiment the method further comprises: depositing additional metal on the second electrode after the annealing step; and patterning the metal to form the second electrode.
Thereby, the whole metal structure, i.e. including the metal deposited as the second electrode and the additional metal, is patterned to form the second electrode.
This enables a larger (thicker) top electrode that may be useful e.g. to enable sufficient optical contrast when probing the ferroelectric device for electrical measurements or for back end of line processing.

Brief description of the drawings
The above, as well as additional objects, features, and advantages of the present inventive concept, will be better understood through the following illustrative and non-limiting detailed description, with reference to the appended drawings. In the drawings like reference numerals will be used for like elements unless stated otherwise.
- Fig. 1a is a schematic illustration of an embodiment of a device layer structure according to the inventive concept.
- Fig. 1b is a schematic illustration of an embodiment of a device layer structure according to the inventive concept.
- Fig. 2 is a schematic illustration of an embodiment of a device layer structure according to the inventive concept.
- Fig. 3 is a schematic illustration of an embodiment of a device according to the inventive concept.
- Fig. 4 is a schematic flowchart of an embodiment of a method according to the inventive concept.
- Fig. 5a is a plot comparing capacitors comprising HZO either with or without Nb_2O_5 capping showing evolution of polarization and current density versus electric field with a number of bipolar fatigue cycles.
- Fig. 5b is a plot showing an evolution of remnant polarization (2P_R) and coercive field with a number bipolar fatigue cycles, demonstrating that a higher remnant polarization (2P_R) and early wake-up may be obtained with an oxide layer comprising Nb_2O_5 on top of HZO.
- Fig. 6a is a plot comparing PUND measurement current density of a metal-HZO-IGZO-metal and metal-HZO- Nb_2O_{5-}IGZO-metal capacitor at two amplitudes of PUND pulses, demonstrating that much higher polarization switching currents may be obtained when HZO is capped with Nb_2O_5.
- Fig. 6b is a plot showing an evolution of remnant polarization versus a number of bipolar fatigue cycles at two amplitudes of bipolar electric field cycling, demonstrating that capping of HZO with Nb_2O_5 offers a very high remnant polarization upon wake-up and prevents fatigue over time.

Detailed description
Fig. 1a illustrates a device layer structure 10 comprising a first electrode 12, a ferroelectric layer 11 of hafnium zirconate (HZO), an oxide layer 21 of Nb_2O_5 or Ta_2O_5 and a second electrode 13.
The oxide layer 21 is arranged on the ferroelectric layer 11, with the oxide layer 21 being in direct contact and above the ferroelectric layer 11. Both the ferroelectric layer 11 and the oxide layer 21 are arranged between the first electrode 12 and the second electrode 13.
Fig. 1b illustrates a similar device layer structure 10, where the oxide layer 21 is arranged on the ferroelectric layer 11, with the oxide layer 21 being in direct contact and under the ferroelectric layer 11.
In another embodiment (not shown), the device layer structure 10 comprises a first and second oxide layer 21, both being arranged on the ferroelectric layer 11. The first oxide layer 21 is arranged in direct contact and under the ferroelectric layer 11. The second oxide layer 21 is arranged in direct contact and above the ferroelectric layer 11.
The following applies to any of these embodiments.
The first electrode 12 may also be referred to as bottom electrode, and the second electrode 13 may also be referred to as a top electrode. Thereby, top and bottom may relate to a fabrication direction or growth direction of the ferroelectric device layer structure 10. Both electrodes 12, 13 may be made of a metal or of a conductive oxide, such as titanium nitride (TiN), titanium, tungsten, or aluminium. The electrodes 12, 13 may have a thickness (in growth direction) of 5-30 nm, such as 10 nm, and may have different thicknesses.
The ferroelectric layer 11 may have at least two non-zero remnant polarization charge states. A thickness (in growth direction) of the ferroelectric layer 11 may be between 3-15 nm, and preferably between 8.5-12.5 nm.
The oxide layer 21 may have majority portion of stoichiometric Nb_2O_5 or Ta_2O_5 and may have a thickness (in growth direction) of 0.5-3 nm, such as 2 nm.
A thickness of 2 nm has been shown to be optimal for a maximized initial 2P_R compared to other thicknesses, i.e. having very good wake-up characteristics.
At least 30%, such as at least 40% and preferably more than 50% or 75% of the ferroelectric layer 11 may have an orthorhombic crystal structure. When the ferroelectric layer 11 has an orthorhombic crystal structure, the different directions that the atoms are separated in (usually) are separated at a different distance. The orthorhombic crystal structure may thereby be said to be strained by definition. The different oxygen atoms are at different distances, which creates a dipole that increases remnant polarization (2P_R).
The added strain from a lattice mismatch between the ferroelectric layer 11 and the oxide layer 21 thereby gives more orthorhombic crystal structure in HZO rather than cubic, monoclinic and triagonal.
At least 30%, such as at least 40% and preferably more than 50% or 75%, of the oxide layer 21 may have an orthorhombic crystal structure. By the oxide layer 21 having an orthorhombic crystal structure, an orthorhombic crystal structure of the ferroelectric layer 11 may be stabilized.
Further, the oxide layer 21 being oxygen-rich may prevent oxygen scavenging by the second electrode 13, which in turn improves endurance. Energy-dispersive X-ray spectroscopy (EDS) has been used to verify that the surface of the oxide layer 21 interfacing with the second electrode 13 has a slightly lower stoichiometric degree of oxygen, which indicates the second electrode 13 scavenging oxygen from the oxide layer 21 instead of the ferroelectric layer 11.
The ferroelectric layer 11 may be doped HZO. The ferroelectric layer 11 is doped with a combination of an element selected from the lanthanide series and/or a rare earth element. Preferably, the elements (dopants) in the doped HZO layer 11 may include one or more of lanthanum, gadolinium, yttrium, scandium, praseodymium.
A total dopant concentration in the doped HZO layer 11 may be equal to or smaller than 2 atomic %, in particular, it may be in a range of 0.7-1.8 atomic %.
The dopants may decrease Ec and reduce leakage.
Fig. 2 illustrates a device layer structure 10 similar to the one in Fig. 1a, the device layer structure 10 further comprising an interfacial layer 31.
The interfacial layer 31 is arranged between the oxide layer 21 and the second electrode 13 in Fig. 2. However, in embodiments similar to the one in Fig. 1b where the oxide layer 21 is arranged below the ferroelectric layer 11, the interfacial layer 31 may be arranged between the oxide layer 21 and the second electrode 12.
The interfacial layer 31 may comprise a layer of a oxide-semiconductor materials (i.e. metallic oxide materials that may be used as semiconductors), such as indium gallium zinc oxide (IGZO), indium tin oxide (ITO), In_2O_3, indium tungsten oxide (IWO).The interfacial layer 31 may comprise a 2D semiconductor layer, like graphene or MX2 (e.g., MoS2), or a layer of another oxide, such as of ZrO_2, or of HfO_2, or of Zr-rich HZO, or of Hf-rich HZO. The interfacial layer 31 may be doped with at least one element from the lanthanide series and/or at least one rare earth element. For example, the interfacial oxide layer 31 may be a ZrO_2 layer and the doped HZO layer 11 may be stoichiometric (50%) or Hf rich (>50%).
The interfacial layer 31 may have a thickness of 4-12 nm.
Fig. 3 illustrates a ferroelectric device 20 comprising a layer structure 10 as described in relation to Figs. 1-2. In particular, the ferroelectric device 20 of Fig. 3 comprises a layer structure 10 comprising an oxide layer 21 arranged above the ferroelectric layer 11 and a second electrode 13 being thicker (in growth direction) and having a different shape than the first electrode 12. In Fig. 3, the first electrode 12 is 10 nm thick and the second electrode 13 is 30 nm thick.
The ferroelectric device 20 may be a metal-ferroelectric-metal (MFM) capacitor, a metal-ferroelectric-semiconductor-metal (MFSM) capacitor, a ferroelectric memory such as a ferroelectric random access memory (FE-RAM) or a ferroelectric flash memory, or a ferroelectric field effect transistor (FeFET).
The ferroelectric device 20 further comprises a doped semiconductor substrate 41. The doped semiconductor substrate 41 has a front side and a back side, wherein the layer structure 10 is arranged on the front side and an aluminium layer 44 is arranged on the back side. The front side is upwards in a stacking direction (i.e. growth direction) and the back side is downwards in Fig. 3, however other variations are also possible.
The doped semiconductor substrate 41 may e.g. be made of boron-doped silicon. The semiconductor substrate may be made of Si, GaAs, sapphire, InP, Germanium, wafer or SOI wafer, or a glass substrate.
The aluminium layer 44 may have a thickness (in growth direction) of 500 nm.
The second electrode 13 may have been patterned to have a different shape than the first electrode 12 and the layer structure 10 as will be described further in relation to Fig. 4.
Fig. 4 shows a flowchart of a method 100 for fabricating a ferroelectric device 20. The ferroelectric device 20 may be as described in relation to Fig. 3. The steps shown are sequential, however another ordering may be possible. Steps shown in dashed lined boxes are optional.
A first step comprises forming S110 a ferroelectric device layer structure. The ferroelectric device layer structure may be as described in relation to Figs. 1-2.
Forming S110 a ferroelectric device layer structure may comprise a number of depositing steps S120-S150. These depositing steps S120-S150 may be performed on a semiconductor substrate, which may be doped.
First, a metal is deposited S120 on a front side of the semiconductor substrate for forming a first electrode. This metal may e.g. be TiN.
Then, HZO is deposited S130 on the metal for forming a ferroelectric layer. The HZO may be doped. The precursors used may be HfCl4, ZrCl4 and H2O or any metalorganic compound with Hf and Zr such as cyclopentadienyl, amidinates, etc.in combination with H_2O, ozone (O_3) or oxygen plasma.
Then, Nb_2O_5 or Ta_2O_5 is deposited S140 on the HZO for forming an oxide layer on the ferroelectric layer. This step S140 may switch ordering with the previous step S130 in another example.
Next, a metal is deposited S150 on the oxide layer. This may form a second electrode and the metal may e.g. be TiN.
The depositing steps S120-S150 may use atomic layer deposition (ALD). This may be any type of ALD, such as plasma enhanced ALD and/or thermal ALD. The reactor temperature for the ALD steps S120-S150 may vary depending on the material deposited. For example, depositing S130 HZO may be done at 300°C and depositing S140 Nb_2O_5 may be done at 250°C.
After forming the ferroelectric device layer structure, the layers of the ferroelectric device layer structure are annealed S160. This comprises heating the ferroelectric device layer structure, e.g. in an annealing oven, to crystallize the layers of the ferroelectric device layer structure. Annealing S160 the layers of the layer structure all at once (i.e. after the layer structure is formed) ensures that the ferroelectric layer and the oxide layer crystallizes simultaneously.
By crystallizing the ferroelectric layer and the oxide layer simultaneously, more of the ferroelectric layer may stabilize with an orthorhombic crystal structure. Accordingly, at least 30% of the ferroelectric layer will have an orthorhombic crystal structure.
To crystallize the oxide layer, the annealing temperature is in a range of 350°C - 750°C if the oxide layer is made of Nb_2O_5 and in a range of 350°C - 900°C if the oxide layer is made of Ta_2O_5. In an embodiment, the annealing temperature is in a range of 400°C - 550°C if the oxide layer is made of Nb_2O_5 and in a range of 350°C - 750°C if the oxide layer is made of Ta_2O_5.
The minimum values of the temperature ranges correspond to a minimum temperature to crystallize the oxide and the maximum values correspond to an appearance of unwanted monoclinic phase into the HZO layer.
After annealing S160, additional metal may be deposited S170 on the metal for forming the second electrode. This metal may be the same as the previously deposited S150 metal and may be performed using ALD.
The metal for forming the second electrode, which may or may not comprise the additional metal deposited S170 in a previous step, may be patterned S180 by e.g. using etching or lithography.
An aluminium layer may be formed S190 on a back side of the semiconductor layer, e.g. using back-side metallization.
Figs. 5a-b show plots comparing a ferroelectric device layer stack according to Figs. 1-3 to a reference.
Fig. 5a shows a plot showing an evolution of polarization and current density when bipolar fatigue cycles with an amplitude between 2.2-2.4V is applied to TiN-HZO (with or without Nb_2O_5 cap)-TiN capacitors, demonstrating wake-up characteristics over time. The larger and less pinched PE curves labeled with Nb_2O_5 correspond to a ferroelectric device (capacitor) comprising a device layer stack comprising HZO capped with Nb_2O_5 according to the present inventive concept and the smaller and more pinched PE curves correspond to a device layer stack without such an oxide layer capping the HZO layer.
The less pinched PE curves in the PE characteristics on the top side of Fig. 5a and the presence of larger and more well-defined current peaks in the IV characteristics on the bottom side of Fig. 5a in the case of a device with HZO capped with Nb_2O_5 that has been cycled once demonstrate improved wake-up characteristics, as these larger current peaks indicate that a larger fraction of the ferroelectric domains have been able to switch at once. Larger current peaks thereby facilitate a clearer distinction between the two different polarization states of the ferroelectric layer.
Fig. 5b shows a plot showing 2P_R and 2Ec as a function of the number of applied bipolar fatigue cycles.
Fig. 5b shows that the remnant polarization (2Pr) of the ferroelectric layer 11 may be maintained at 10 µC/cm^2 or even higher, when the endurance is equal to or greater than 1E+5 cycles, or greater than 1E+9 cycles, or even greater than 1E+11 cycles. In particular, an almost fatigue free behaviour with a remnant polarization (2Pr) of above 20 µC/cm^2 or a fatigue free behaviour with a remnant polarization (2Pr) of at least 24 µC/cm^2 may be achieved in the ferroelectric device layer structure.
Such a large remnant polarization (2Pr) may further mean that an area of the ferroelectric device layer structure may be reduced without sacrificing a differentiation of the polarization states of the ferroelectric layer.
Accordingly, the oxide layer is shown to greatly improve fatigue resistance, i.e. around 70% improvement at 1E+11 cycles.
Figs. 6a-b show plots comparing a ferroelectric device layer stack according to Figs. 1-3 to a reference. The ferroelectric device layer stack of Figs. 6a-b and the reference layer stack further comprise an interfacial layer as in Fig. 2.
Fig. 6a shows a plot showing a comparison of PUND measurement on TiN-HZO (with or without Nb_2O_5 cap)- IGZO-TiN capacitors at two amplitudes (3.2 and 4.2 MV/cm) of measurement pulses. Different (switching and non-switching PUND) pulses are shown overlapping each other, with different amplitudes in the left-hand side compared to the right-hand side of Fig. 6a. The bottommost plots correspond to a device layer stack comprising Nb_2O_5 according to the present inventive concept and the topmost plots correspond to a device layer stack without such an oxide layer.
The larger current peaks in the bottom most plots indicate that a larger number of ferroelectric domains are available for switching when HZO is capped with Nb_2O_5.
Fig. 6b shows a plot showing 2P_R versus a number of cycles, demonstrating fatigue resistance over time. The topmost data points correspond to a device layer stack comprising Nb_2O_5 according to the present inventive concept and the lowermost data points correspond to a device layer stack without such an oxide layer.
The data points not trending downwards indicate an improved fatigue resistance.
In the above the inventive concept has mainly been described with reference to a limited number of examples. However, as is readily appreciated by a person skilled in the art, other examples than the ones disclosed above are equally possible within the scope of the inventive concept, as defined by the appended claims.
1. A ferroelectric device layer structure (10) comprising:
a first electrode (12) and a second electrode (13);
a ferroelectric layer (11) of hafnium zirconate, HZO; and
an oxide layer (21) of Nb_2O_5 or Ta_2O_5 arranged on the ferroelectric layer (11);
wherein the ferroelectric layer (11) and the oxide layer (21) are arranged between the first electrode (12) and the second electrode (13).
2. A device layer structure according to claim 1, wherein at least 30% of the ferroelectric layer (11) and the oxide layer (21) has an orthorhombic crystal structure.
3. A device layer structure according to claim 1 or 2, further comprising an interfacial layer (31), which is arranged between the oxide layer (21) and the second electrode (13).
4. A device layer structure according to any one of the preceding claims, wherein the ferroelectric layer (11) is a doped HZO layer.
5. A device layer structure according to any one of the preceding claims, wherein the oxide layer (21) is between 0.5-3 nm thick.
6. A ferroelectric device (20) comprising the layer structure (10) according to any one of the preceding claims, further comprising a doped semiconductor substrate (41) having a front side and a back side, wherein the layer structure (10) is arranged on the front side.
7. A method (100) for fabricating a ferroelectric device (20), wherein the method (100) comprises:
forming (S110) a ferroelectric device layer structure (10) comprising:
a first electrode (12) and a second electrode (13);
a ferroelectric layer (11) of hafnium zirconate, HZO; and
an oxide layer (21) of Nb_2O_5 or Ta_2O_5 arranged on the ferroelectric layer (11);
wherein the ferroelectric layer (11) and the oxide layer (21) are arranged between the first electrode (12) and the second electrode (13); the method further comprising:
annealing (S160) the layers of the ferroelectric device layer structure (10) at a temperature in a range of 350°C - 750°C if the oxide layer (21) is made of Nb_2O_5 and in a range of 350°C - 900°C if the oxide layer (21) is made of Ta_2O_5.
8. A method according to claim 7,wherein forming (S110) a ferroelectric device layer structure (10) comprises:
depositing (S120) a metal for forming the first electrode (12) on a front side of a semiconductor substrate (41);
depositing (S130) HZO for forming the ferroelectric layer (11) on the first electrode (12);
depositing (S140) Nb_2O_5 or Ta_2O_5 for forming the oxide layer (21) on the ferroelectric layer (11); and then
depositing (S150) a metal for forming the second electrode (12).
9. A method according to claim 8, further comprising forming (S190) an aluminium layer (44) on a back side of the semiconductor substrate (41).
10. A method according to claim 8 or 9, wherein the depositing steps (S120, S130, S140, S150) use atomic layer deposition, ALD.
11. A method according to claim 10, wherein the ALD is performed with a reactor temperature in a range of 150°C - 450°C.
12. A method according to any one of the claims 6-10, further comprising:
depositing (S170) additional metal on the second electrode (13) after the annealing step (S160); and
patterning (S180) the metal to form the second electrode (13).
EP-21131572
EP
21216277.0
IMEC VZW
1a
MN
20220519
H01L
HOFFMANN MICHAEL ET AL
Unveiling the double-well energy landscape in a ferroelectric layer
NATURE, NATURE PUBLISHING GROUP UK, LONDON
20190114
565
7740
10.1038/S41586-018-0854-Z
0028-0836
464
467
XP036683782
X
1,2,4-12
A
3
* the whole document *
GADDAM VENKATESWARLU ET AL
Ferroelectricity Enhancement in Hf0.5Zr0.5O2 Capacitors by Incorporating Ta2O5 Dielectric Seed Layers
2020 4TH IEEE ELECTRON DEVICES TECHNOLOGY & MANUFACTURING CONFERENCE (EDTM), IEEE
20200406
10.1109/EDTM47692.2020.9117881
1
3
XP033780662
X
1,2,4-12
A
3
* chapter 'II. Expiermental' *
US
2020350324
A1
HOFFMANN MICHAEL [DE]
20201105
X
1,2,4-12
A
3
* paragraph [0021] - paragraph [0034] *
* paragraph [0041] *
* paragraph [0047] *
* figures 4, 6 *
CHOU CHUAN-PU ET AL
Junctionless Poly-GeSn Ferroelectric Thin-Film Transistors with Improved Reliability by Interface Engineering for Neuromorphic Computing
APPLIED MATERIALS & INTERFACES
US
20200108
12
1
10.1021/acsami.9b16231
1944-8244
1014
1023
XP055918675
X
1-12
* page 1020-1021, chapter 'Experimental section' *
HOFFMANN MICHAEL ET AL
Progress and future prospects of negative capacitance electronics: A materials perspective
APL MATERIALS, AMERICAN INSTITUTE OF PHYSICS, 2 HUNTINGTON QUADRANGLE, MELVILLE, NY 11747
20210211
9
2
10.1063/5.0032954
XP012253963
A
1-12
* the whole document *
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JOM: JOURNAL OF METALS, SPRINGER NEW YORK LLC, UNITED STATES
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71
1
10.1007/S11837-018-3140-5
1047-4838
246
255
XP036663722
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1-12
Bruckmayer, Manfred
Munich
20220509
US
2020350324
A1
20201105
DE
102019003223
A1
20201105
US
2020350324
A1
20201105